Method and reactor for cracking hydrocarbon

ABSTRACT

A method for cracking hydrocarbon, comprises: providing steam and hydrocarbon; and feeding steam and hydrocarbon into a reactor accessible to hydrocarbon and comprising a perovskite material of formula A a B b C c D d O 3−δ , wherein 0&lt;a&lt;1.2, 0≤b≤1.2, 0.9&lt;a+b≤1.2, 0&lt;c&lt;1.2, 0≤d≤1.2, 0.9&lt;c+d≤1.2, −0.5&lt;δ&lt;0.5; A is selected from calcium, strontium, barium, and any combination thereof; B is selected from lithium, sodium, potassium, rubidium and any combination thereof; C is selected from cerium, zirconium, antimony, praseodymium, titanium, chromium, manganese, ferrum, cobalt, nickel, gallium, tin, terbium and any combination thereof; and D is selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, titanium, vanadium, chromium, manganese, ferrum, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, gallium, indium, tin, antimony and any combination thereof.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No. 13/115,610 filed May 25, 2011, which in turn claims priority benefit under 35 USC § 119 of Chinese Patent Application No. 201010192512.4 filed May 31, 2010.

BACKGROUND

The invention relates generally to methods and reactors for cracking hydrocarbon. More specifically, the invention relates to methods and reactors for cracking hydrocarbon, in which the build-up of coke deposits are undesirable.

In the petrochemical industry, hydrocarbons such as ethane, propane, butane and naphtha are cracked in reactors, in the presence of from about 30 to 70 weight percentage of steam, at temperatures of from about 700° C. to 870° C. in order to produce light olefins such as ethylene and propylene. Sometimes, hydrocarbons such as bottoms from atmospheric and vacuum distillation of crude oil are cracked in reactors at a temperature in a range from about 480° C. to about 600° C. in the presence of about 1 wt % to about 2 wt % steam.

During hydrocarbon cracking processes, the build-up of carbonaceous deposits (i.e. coke deposits) usually happens on inner surfaces of reactor components, for instance, inner radiant tube surfaces of furnace equipment. The inner radiant tube surfaces become gradually coated with a layer of coke which raises the radiant tube metal temperature (TMT) and increases the temperature drop through radiant coils. In addition, coke build-up adversely affects the physical characteristics of the reactor components, such as the radiant tubes, by deteriorating mechanical properties such as stress rupture, thermal fatigue, and ductility.

In order to decoke reactor components, the reactor must be periodically shut down. Typically, the decoking is carried out by combustion of the coke deposits with steam/air at temperatures of up to 1000° C. Such decoking operations are required approximately every 10 to 80 days, depending on the operation mode, types of hydrocarbons and hydrocarbons throughput, and result in production loss since hydrocarbons feeding must be stopped for such decoking operation.

A variety of methods have been considered in order to overcome the disadvantages of coke build-up on reactor components, such as furnace tube inner surfaces. These approaches include: metallurgy upgrade to alloys with increased chromium content of the metal substrates used in the furnaces; adding additives such as sulfur, dimethyl sulfide (DMS), dimethyl disulfide (DMDS) or hydrogen sulfide to the feedstock; increasing steam dilution of feedstock, and improved process control; selectively pre-treating the inner surface of the coils; inert surface coating; and catalytic gasification of coke to produce CO/CO₂ and hydrogen.

While some of the aforementioned methods and systems have general use in the petrochemical industry, it is desirable to provide a method and reactor that obviates and mitigates the shortcomings of the prior art and successfully reduces or eliminates the build-up of coke deposits.

BRIEF DESCRIPTION

In one aspect, the invention relates to a method for cracking hydrocarbon, comprising: providing steam and hydrocarbon; and feeding steam and hydrocarbon into a reactor having an inner surface accessible to hydrocarbon, the inner surface comprising a perovskite material of formula A_(a)B_(b)C_(c)D_(d)O_(3−δ), wherein 0<a<1.2, 0=<b<=1.2, 0.9<a+b≤1.2, 0<c<1.2, 0≤.d≤1.2, 0.9<c+d≤1.2, −0.5<δ<0.5; A is selected from calcium (Ca), strontium (Sr), barium (Ba), and any combination thereof; B is selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and any combination thereof; C is selected from cerium (Ce), zirconium (Zr), antimony (Sb), praseodymium (Pr), titanium (Ti), chromium (Cr), manganese (Mn), ferrum (iron?) (Fe), cobalt (Co), nickel (Ni), gallium (Ga), tin (Sn), terbium (Tb) and any combination thereof; and D is selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), ferrum (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), gallium (Ga), indium (In), tin (Sn), antimony (Sb) and any combination thereof.

In another aspect, the invention relates to a reactor for cracking hydrocarbon having an inner surface accessible to the hydrocarbon, the inner surface comprising a perovskite material of formula A_(a)B_(b)C_(c)D_(d)O_(3-δ), wherein 0<a<1.2, 0.9<a+b≤1.2, 0<c<1.2, 0≤d≤1.2, 0.9<c+d≤1.2, −0.5<δ<0.5; A is selected from calcium (Ca), strontium (Sr), barium (Ba), and any combination thereof; B is selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and any combination thereof; C is selected from cerium (Ce), zirconium (Zr), antimony (Sb), praseodymium (Pr), titanium (Ti), chromium (Cr), manganese (Mn), ferrum (Fe), cobalt (Co), nickel (Ni), gallium (Ga), tin (Sn), terbium (Tb) and any combination thereof; and D is selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), ferrum (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), gallium (Ga), indium (In), tin (Sn), antimony (Sb) and any combination thereof.

DRAWINGS

These and other features, aspects, and advantages of the present invention will become better understood when the following detailed description is read with reference to the accompanying drawings, wherein:

FIG. 1 shows the weight reduction percentages of the carbon black in the sample 1 and sample 2 after the sample 1 and the sample 2 were exposed to the helium-steam mixture compared with before exposure at different temperatures;

FIG. 2 shows the concentration of carbon dioxide generated after the sample 1 and the sample 2 were exposed to the helium-steam mixture at different temperatures; and

FIG. 3 shows the weight reduction percentages of carbon black in samples 3-13 after the samples 3-13 were exposed to the helium-steam mixture with respect to before exposure at different temperatures.

DETAILED DESCRIPTION

In one aspect, the invention relates to a method for cracking hydrocarbon, comprising: providing steam and hydrocarbon; and feeding steam and hydrocarbon into a reactor having an inner surface accessible to hydrocarbon, the inner surface comprising a perovskite material of formula A_(a)B_(b)C_(c)D_(d)O_(3-δ), wherein 0<a<1.2, 0 b≤1.2, 0.9<a+b≤1.2, 0<c<1.2, 0≤d≤1.2, 0.9<c+d≤1.2, −0.5<δ<0.5; A is selected from calcium (Ca), strontium (Sr), barium (Ba), and any combination thereof, B is selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and any combination thereof; C is selected from cerium (Ce), zirconium (Zr), antimony (Sb), praseodymium (Pr), titanium (Ti), chromium (Cr), manganese (Mn), ferrum (Fe), cobalt (Co), nickel (Ni), gallium (Ga), tin (Sn), terbium (Tb) and any combination thereof, and D is selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), ferrum (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), gallium (Ga), indium (In), tin (Sn), antimony (Sb) and any combination thereof.

In another aspect, the invention relates to a reactor for cracking hydrocarbon having an inner surface accessible to the hydrocarbon, the inner surface comprising a perovskite material of formula A_(a)B_(b)C_(c)D_(d)O_(3-δ), wherein 0<a<1.2, 0≤b≤1.2, 0.9<a+b≤1.2, 0<c<1.2, 0≤d≤1.2, 0.9<c+d≤1.2, −0.5<δ<0.5; A is selected from calcium (Ca), strontium (Sr), barium (Ba), and any combination thereof, B is selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and any combination thereof; C is selected from cerium (Ce), zirconium (Zr), antimony (Sb), praseodymium (Pr), titanium (Ti), chromium (Cr), manganese (Mn), ferrum (Fe), cobalt (Co), nickel (Ni), gallium (Ga), tin (Sn), terbium (Tb) and any combination thereof; and D is selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), ferrum (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), gallium (Ga), indium (In), tin (Sn), antimony (Sb) and any combination thereof.

In some embodiments, A is selected from strontium (Sr) and barium (Ba). C is selected from cerium (Ce), zirconium (Zr), and manganese (Mn). D is selected from cerium (Ce) and yttrium (Y).

In some embodiments, the perovskite material is selected from SrCeO_(3,) SrZr_(0.3)Ce_(0.7)O₃, BaMnO_(3,) BaCeO_(3,) BaZr_(0.3)Ce_(0.7)O_(3,) BaZr_(0.3)Ce_(0.5)Y_(0.2)O_(3,) BaZr_(0.1)Ce_(0.7)Y_(0.2)O_(3,) BaZrO_(3,) BaZr_(0.7)Ce_(0.3)O_(3,) BaCe_(0.5)Zr_(0.5)O_(3,) BaCe_(0.9)Y_(0.1)O_(3,) BaCe_(0.85)Y_(0.15)O_(3,) and BaCe_(0.8)Y_(0.2)O_(3.) For example, for SrCeO_(3,) A is Sr, C is Ce, a=1, b=0, c=1, d=0, and δ=0. For SrZr_(0.3)Ce_(0.7)O_(3,) A is Sr, C is Zr, D is Ce, a=1, b=0, c=0.3, d=0.7, and δ=0. For BaMnO_(3,) A is Ba, C is Mn, a=1, b=0, c=1, d=0, and δ=0. For BaCeO_(3,) A is Ba, C is Ce, a=1, b=0, c=1, d=0, and 8=0. For BaZr_(0.3)Ce_(0.7)O_(3,) A is Ba, C is Zr, D is Ce, a=1, b=0, c=0.3, d=0.7, and δ=0. For BaZr_(0.3)Ce_(0.5)Y_(0.2)O_(3,) A is Ba, C is Zr, D is combination of Ce and Y, a=1, b=0, c=0.3, d=0.7, and δ=0. As one of ordinary skill in the art can understand from the above, more examples are omitted here to avoid obscuring the disclosure in unnecessary details.

In some embodiments, the method is operated at a temperature in a range from about 700° C. to about 870° C., a weight ratio of steam to hydrocarbon is in a range from about 3:7 to about 7:3, and the hydrocarbon comprises at least one of ethane, heptane, liquid petroleum gas, naphtha, and gas oil.

In some embodiments, the method is operated at a temperature in a range from about 480° C. to about 600° C., wherein the hydrocarbon comprises bottoms from atmospheric and vacuum distillation of crude oil and the mixture comprises from about 1 wt % to about 2 wt % steam.

In some embodiments, the perovskite material is SrZr_(0.3)Ce_(0.2)O₃.

In some embodiments, the perovskite material is BaZr_(0.3)Ce_(0.2)O₃.

In some embodiments, the perovskite material is BaZr_(0.1)Ce_(0.7)Y_(0.2)O₃.

In some embodiments, the perovskite material is BaCe_(0.8)Y_(0.2)O₃.

The perovskite material may be a coating applied using different methods, for example, air plasma spray, slurry coating, sol-gel coating, and solution coating. In some embodiments, the perovskite material is coated using air plasma spray method.

The reactor may be any reactor in which hydrocarbon is cracked. In some embodiments, the reactor comprises at least one of a furnace tube, a tube fitting, a reaction vessel, and a radiant tube.

Definitions

As used herein, the term “reactor” refers to but is not limited to at least one of a furnace tube, a tube fitting, a reaction vessel, and a radiant tube, used in petrochemical processes.

As used herein the term “cracking hydrocarbon” refers to but is not limited to processes in which hydrocarbons such as ethane, propane, butane and naphtha are cracked in reactors, in the presence of from about 30 to 70 weight percentage of steam, at temperatures of from about 700° C. to 870° C. in order to produce light olefins such as ethylene and propylene. Sometimes, hydrocarbons such as bottoms from atmospheric and vacuum distillation of crude oil are cracked in reactors at a temperature in a range from about 480 to about 600° C. in the presence of about 1 wt % to about 2 wt % steam.

As used herein the term “coke” refers to but is not limited to carbonaceous solid or liquid or particulates or macromolecules forming the carbonaceous solid or liquid, which are derived from coal, petroleum, wood, hydrocarbons and other materials containing carbon and which include, for example, carbon black, tar, and pyrolytic coke existing in hydrocarbon cracking furnace.

Any numerical values recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value. As an example, if it is stated that the amount of a component or a value of a process variable such as, for example, temperature, pressure, time and the like is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc. are expressly enumerated in this specification. For values which are less than one, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application in a similar manner.

EXAMPLES

The following examples are included to provide additional guidance to those of ordinary skill in the art in practicing the claimed invention. Accordingly, these examples do not limit the invention as defined in the appended claims.

A lab scale hydrocarbon-cracking furnace was built up. Due to structure similarity of naphtha, heptane was used as the source of hydrocarbon.

Samples on quartz sample holders were placed at the constant temperature region of the cracking furnace. The furnace door was then closed. Argon gas was fed in the furnace at the flow rate of 100 standard cubic centimeter per minute (sccm). The cracking furnace was heated to 880° C. with the ramping rate of 20° C./min. A vaporizer was heated to 350° C. within 30 minutes.

When the temperature of the cracking furnace reached 880° C. and the temperature of the vaporizer reached 350° C., water was pumped using a piston pump into the vaporizer with the flow rate of 1.58 ml/min. Argon gas feeding was stopped. After 5 minutes, heptane was pumped using a piston pump into the vaporizer with the flow rate of 2.32 ml/min to be vaporized and mixed with the steam in the vaporizer in a 1:1 weight ratio. The temperature of the cracking furnace was maintained at desired temperature, e.g., 800+/−5° C. or 860+/−5° C. for desired time before stopping the pumpings of the heptane and water. The residence time of the heptane and steam in the cracking furnace was 1.5 seconds, unless otherwise specified. Argon gas was fed again at the flow rate of 100 sccm before the cracking furnace and the vaporizer were shut down. When the cracking furnace cooled down, argon gas feed was stopped and the furnace door was opened to take out the sample holders.

Comparative Example

Square pellets each with the dimension of 6×6×1 mm³ made of materials commonly used in hydrocarbon-cracking reactors, i.e., 310S, incoloy 800 HT, incoloy 825, Al₂O_(3,) SiN_(x), SiC and SiO₂ were used as samples. Compositions of the alloy pellets, i.e., 310S, incoloy 800HT, and incoloy 825 are shown in Table 1 below. Electric balance was used to measure the weight of each pellet before and after cracking experiment. Weights of cokes deposited on the pellets changed with time and are shown in Table 2 below.

TABLE 1 r i e n i u o l i wt %) wt %) wt %) wt %) wt %) wt %) wt %) wt %) wt %) wt %) wt %) wt %) 310S 5.6 8.9 2 .6 .4 .5 Incoloy 0.62 0.76 5.57 .89 .65 .005 .29 .57 .56 .082 800HT Incoloy 0.80 1.07 1.22 .51 .32 .003 .020 .02 .95 .20 .89 .015 825

TABLE 2 incoloy incoloy time 310S 800HT 825 Al₂O₃ SiN_(x) SiC SiO₂ (hour(s)) (g) (g) (g) (g) (g) (g) (g) 0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 2 0.23 0.35 0.29 2.5 0.17 0.18 0.16 0.17 4 0.38 0.50 0.45 4.5 0.31 0.34 0.30 0.29 6 0.59 0.74 0.80 8 0.81 0.98 0.75 0.56 0.58 0.62 10 0.90 1.05 0.97 0.65 0.77 0.70

Example 1

The perovskite materials were prepared by solid state reaction method. Using BaZr_(0.3)Ce_(0.5)Y_(0.2)O₃ as an example, stoichiometric amounts of high-purity barium carbonate, zirconium oxide, cerium oxide, and yttrium oxide powders (all from Sinopharm Chemical Reagent Co., Ltd. (SCRC), Shanghai, China) were mixed in ethanol and ball-milled for 12 hours. The resultant mixtures were then dried and calcined at 1100° C. in air for 6 hours to form the perovskite powder. The powder was iso-statically pressed at 274.6 MPa for 10 minutes to become a disk. The disk was then sintered at 1400° C. for 6 hours in air. The sintered disk was polished to have a thickness of 1 mm. The perovskite phase was confirmed using an X-ray diffractometer (D8 Advance, Bruker AXS GmbH, Karlsruhe, Germany).

Example 2

Disks made from SrCeO_(3,) SrZr_(0.7)Ce_(0.7)O_(3,) BaMnO_(3,) BaCeO_(3,) BaZr_(0.3)Ce_(0.7)O_(3,) and Al₂O₃ and having a thickness of 1 mm and a diameter of 10 mm were used as samples and stayed in the cracking furnace at 800° C.+/−5° C. for 2 hours. No coke depositions were observed on surfaces of the SrCeO₃ disk, the SrZr_(0.3)Ce_(0.7)O₃ disk, the BaMnO₃ disk, the BaCeO₃ disk, and the BaZr_(0.3)Ce_(0.7)O₃ disk while the coke deposition was observed on the Al₂O₃ disk.

The X-ray Diffraction (XRD) results of the BaZr_(0.3)Ce_(0.7)O₃ disk before and after the experiment demonstrate that this material is rather stable in the experiment.

Example 3

Disks of 1 mm thick and 10 mm diameter made from BaCO_(3,) BaTiO_(3,) the mixture of CeO₂ and BaCO_(3,) and Al₂O_(3,) respectively, were used as samples and stayed in the cracking furnace at 800° C. for 2 hours. It was found that small amount of coke appeared on the surface of BaCO₃ disk, relatively more cokes were deposited on the BaTiO₃ and Al₂O₃ disks, and no coke was deposited on the CeO₂ and BaCO₃ mixture disk. XRD characterization shows that the perovskite material BaCeO₃ was formed from the CeO₂ and BaCO₃ mixture in-situ during the experiment. It suggests that the perovskite material BaCeO₃ with Ba on A site and Ce on C site has higher anti-coking performance than BaCO_(3,) BaTiO₃ and Al₂O₃.

Example 4

A coupon made from alloy 310S with the dimension of 10×30×1 mm³ was used as the substrate. Before coating, the substrate was cleaned carefully as follows: ultrasonic agitation in acetone and ethanol for 30 minutes, respectively, to remove organic contaminants, ultrasonic agitation in HCl (3.3 wt %) aqueous solution for 30 minutes to etch the substrate surface, ultrasonically rinsing in DI-water, and finally dried completely by compressed air. After ball milling and granulation process to make the average size of BaZr_(0.1)Ce_(0.7)Y_(0.2)O₃ powders to be around 20 micrometers, the powders were fed in an air plasma spray system to deposit BaZr_(0.1)Ce_(0.7)Y_(0.2)O₃ coating on the fully cleaned 310S substrate. XRD results identified the perovskite phase of BaCe_(0.7)Zr_(0.1)Y_(0.2)O₃ in the coating.

Example 5

The coated alloy coupon obtained in Example 4 was then used as a sample and stayed in the cracking furnace at 860° C. for 8 hours in the heptane/steam (1:1 wt) mixture. It was observed that no coke was formed on the BaZr_(0.1)Ce_(0.7)Y_(0.2)O₃ film. Energy disperse spectroscopy (EDS) analysis was performed after the experiment and confirmed that no carbon can be identified on the surface of the BaZr_(0.1)Ce_(0.7)Y_(0.2)O₃ film. However, black carbon was observed on the blank section of the alloy substrate without the BaZr_(0.1)Ce_(0.7)Y_(0.2)O₃ film. This experiment suggests that the BaZr_(0.1)Ce_(0.7)Y_(0.2)O₃ film is effective for anti-coking.

Example 6

Sample 1 (the mixture of carbon black and BaZr_(0.3)Ce_(0.7)O₃ powders with a weight ratio of 1:10, total weight: 330 mg) and sample 2 (the carbon black powder, 30 mg) were tested in 50:50 (vol) helium:steam mixture using a thermogravimetric analyzer (TGA) (TG 151, from Calm Instruments, Inc., Cerritos, Calif., USA). The heating rate of TGA was 5° C./min, and the temperature range was 400° C. to 950° C. The weights of the samples were measured at different temperatures. The weight reduction percentages of carbon black in the samples were calculated out and shown in FIG. 1. Nicoler™ 380 FT-IR spectrometer from Thermo Electron Scientific Instruments Corp., Madison, Wis., USA was used to analyze the concentration of generated carbon dioxide at different temperatures. The concentrations of carbon dioxide at different temperatures are shown in FIG. 2.

FIG. 1 shows that more carbon black was consumed in the sample 1 than in the sample 2, especially when the temperature is around and higher than 800° C. FIG. 2 shows that more carbon dioxide were generated from the sample 1 than from the sample 2. The experiment suggests that the BaZr_(0.3)Ce_(0.7)O₃ may be used in the temperature range of 400° C. to 950° C. where coke formation/existence is not desired.

Example 7

Samples 3-13 were tested in 50:50 (vol) helium:steam mixture by using TGA. Samples 3-5 and 7-13 are powder mixtures of carbon black with BaZr_(0.3)Ce_(0.7)O_(3,) BaCeO_(3,) BaCe_(0.5)Zr_(0.5)O_(3,) BaZr_(0.7)Ce_(0.3)O_(3,) BaZrO_(3,) BaZr_(0.1)Ce_(0.7)Y_(0.2)O_(3,) BaCe_(0.85)Y_(0.15)O_(3,) BaCO_(3,) BaCe_(0.9)Y_(0.1)O_(3,) and BaCe_(0.8)Y_(0.2)O₃ respectively (weight ratio of 1:10, total weight: 330 mg). Sample 6 was carbon black powder (30 mg). The heating rate of TGA was 5° C./min, and the temperature range was from about 400° C. to about 950° C. The weight reduction percentages of carbon black in the samples were calculated out and shown in FIG. 3.

FIG. 3 shows more carbon black was consumed in the samples 3-5 and 7-13 than in the sample 6, especially when the temperature is around and higher than 785° C. It suggests that BaZr_(0.3)Ce_(0.7)O_(3,) BaCeO_(3,) BaCe_(0.5)Zr_(0.5)O_(3,) BaZr_(0.3)Ce_(0.7)O_(3,) BaZrO_(3,) BaZr_(0.1)Ce_(0.7)Y_(0.2)O_(3,) BaCe_(0.85)Y_(0.15)O_(3,) BaCO_(3,) BaCe_(0.9)Y_(0.1)O₃ and BaCe_(0.8)Y_(0.2)O₃ may be used in the temperature range of 400° C. to 950 ° C. where the coke formation/existence is not desired.

While only certain features of the invention have been illustrated and described herein, many modifications and changes will occur to those skilled in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit of the invention. 

The invention claimed is:
 1. A method for inhibiting coke deposit formation in a hydrocarbon cracking reactor having an inner surface accessible to said hydrocarbon and wherein a hydrocarbon feedstock comprising ethane is cracked in the presence of steam to form ethylene, said inner surface comprising a perovskite material of formula A_(a)B_(b)C_(c)D_(d)O_(3−δ), wherein 0<a<1.2, 0≤b≤1.2, 0.9<a+b≤1.2, 0<c<1.2, 0.0≤d≤1.2, 0.9<c+d≤1.2, −0.5<δ<0.5; A is selected from calcium (Ca), strontium (Sr), barium (Ba), and any combination thereof; B is selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and any combination thereof; C is selected from cerium (Ce), zirconium (Zr), antimony (Sb), praseodymium (Pr), titanium (Ti), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), gallium (Ga), tin (Sn), terbium (Tb) and any combination thereof; and D is selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), palladium (Pd), silver (Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), gallium (Ga), indium (In), tin (Sn), antimony (Sb) and any combination thereof, said perovskite material gasifying said coke to produce CO, CO₂, and hydrogen.
 2. The method of claim 1, wherein A is selected from strontium (Sr) and barium (Ba).
 3. The method of claim 1, wherein C is selected from cerium (Ce), zirconium (Zr), and manganese (Mn).
 4. The method of claim 1, wherein D is selected from cerium (Ce) and yttrium (Y).
 5. The reactor of claim 1, wherein the perovskite material is selected from SrCeO₃, SrZr_(0.3)Ce_(0.7)O₃, BaMnO₃, BaCeO₃, BaZr_(0.3)Ce_(0.5)Y_(0.2)O₃, BaZr_(0.1)Ce_(0.7)Y_(0.2)O₃, BaZrO₃, BaCe_(0.9)Y_(0.1)O₃, BaCe_(0.85)Y_(0.15)O₃, and BaCe_(0.8)Y_(0.2)O₃.
 6. The method of claim 1, being operated at a temperature in a range from about 700° C. to about 870° C. and wherein a weight ratio of steam to hydrocarbon feedstock is in a range from about 3:7 to about 7:3.
 7. The method as recited in claim 1 wherein said perovskite material is devoid of samarium (Sm), ruthenium (Ru) or rhodium (Rh).
 8. The method of claim 1, wherein said hydrocarbon cracking reactor is operated at a temperature in a range from about 480 to about 600° C.
 9. The method of claim 1, wherein the perovskite material is SrZr_(0.3)Ce_(0.7)O₃.
 10. The method of claim 1, wherein the perovskite material is BaZr_(0.1)Ce_(0.7)Y_(0.2)O₃.
 11. The method of claim 1, wherein the perovskite material is BaCe_(0.8)Y_(0.2)O₃.
 12. A method for inhibiting coke deposit formation in a hydrocarbon cracking reactor having an inner surface accessible to said hydrocarbon and wherein a hydrocarbon feedstock comprising ethane is cracked in the presence of steam to form ethylene, said inner surface comprising a perovskite material of formula A_(a)B_(b)C_(c)D_(d)O_(3−δ), wherein 0<a<1.2, 0≤b≤1.2, 0.9<a+b≤1.2, c is present in an amount of <1.2, 0≤d≤1.2, 0.9<c+d≤1.2, −0.5<δ<0.5; A is selected from calcium (Ca), strontium (Sr), barium (Ba), and any combination thereof; B is selected from lithium (Li), sodium (Na), and potassium (K), and any combination thereof; C is a combination of cerium (Ce) and zirconium (Zr); and D is selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), ebium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), palladium (Pd), silver (Ag), cadmium (Cd), hafnium (HO, tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), gallium (Ga), indium (In), tin (Sn), antimony (Sb) and any combination thereof; said perovskite material gasifying said coke to produce CO, CO₂, and hydrogen.
 13. The method as recited in claim 12 wherein said method is conducted at a temperature of between about 480° C. to about 870° C.
 14. The method as recited in claim 12 being operated at a temperature in a range of from about 700° C. to about 870° C. and wherein a weight ratio of steam to hydrocarbon feedstock is in a range of about 3:7 to about 7:3.
 15. The method as recited in claim 12 wherein said perovskite material is applied to said inner surface as a coating.
 16. The method as recited in claim 12 wherein said perovskite material is present in the form of a pressed powder.
 17. The method as recited in claim 12 wherein said perovskite material is devoid of samarium (Sm), ruthenium (Ru) or rhodium (Rh).
 18. The method as recited in claim 12 wherein said inner surface is devoid of Ni.
 19. The method as recited in claim 12 wherein said perovskite material is selected from the group consisting of SrZr_(0.3)Ce_(0.7)O₃, BaZr_(0.3)Ce_(0.5)Y_(0.2)O₃, and BaZr_(0.1)Ce_(0.7)Y_(0.2)O₃.
 20. The method as recited in claim 19 wherein said perovskite material is SrZr_(0.3)Ce_(0.7)O₃.
 21. The method as recited in claim 19 wherein said perovskite material is BaZr_(0.3)Ce_(0.5)Y_(0.2)O₃.
 22. The method as recited in claim 19 wherein said perovskite material is BaZr_(0.1)Ce_(0.7)Y_(0.2)O₃. 